CN102203211A - A proppant - Google Patents
A proppant Download PDFInfo
- Publication number
- CN102203211A CN102203211A CN2009801432762A CN200980143276A CN102203211A CN 102203211 A CN102203211 A CN 102203211A CN 2009801432762 A CN2009801432762 A CN 2009801432762A CN 200980143276 A CN200980143276 A CN 200980143276A CN 102203211 A CN102203211 A CN 102203211A
- Authority
- CN
- China
- Prior art keywords
- coating
- poly
- propping agent
- particle
- isocyanic ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000576 coating method Methods 0.000 claims abstract description 300
- 239000011248 coating agent Substances 0.000 claims abstract description 289
- 239000002245 particle Substances 0.000 claims abstract description 187
- 239000012948 isocyanate Substances 0.000 claims abstract description 71
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 215
- 150000001718 carbodiimides Chemical class 0.000 claims description 143
- 150000002148 esters Chemical class 0.000 claims description 97
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 45
- 239000012530 fluid Substances 0.000 claims description 39
- 239000004576 sand Substances 0.000 claims description 37
- -1 phosphorus compound Chemical class 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 125000005442 diisocyanate group Chemical group 0.000 claims description 27
- 230000001737 promoting effect Effects 0.000 claims description 21
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 17
- 244000005700 microbiome Species 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 101001105692 Homo sapiens Pre-mRNA-processing factor 6 Proteins 0.000 claims description 9
- 102100021232 Pre-mRNA-processing factor 6 Human genes 0.000 claims description 9
- 150000001408 amides Chemical class 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
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- 238000003723 Smelting Methods 0.000 claims description 4
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- 239000003610 charcoal Substances 0.000 claims description 4
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- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
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- BRDWIEOJOWJCLU-LTGWCKQJSA-N GS-441524 Chemical group C=1C=C2C(N)=NC=NN2C=1[C@]1(C#N)O[C@H](CO)[C@@H](O)[C@H]1O BRDWIEOJOWJCLU-LTGWCKQJSA-N 0.000 claims 1
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- 206010017076 Fracture Diseases 0.000 description 26
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- 238000012360 testing method Methods 0.000 description 21
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- 239000011527 polyurethane coating Substances 0.000 description 19
- 239000003921 oil Substances 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
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- 239000004202 carbamide Substances 0.000 description 16
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- 239000000446 fuel Substances 0.000 description 15
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 15
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- 238000001914 filtration Methods 0.000 description 13
- 150000002989 phenols Chemical class 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 238000005054 agglomeration Methods 0.000 description 12
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- 150000001412 amines Chemical class 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
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- 238000005516 engineering process Methods 0.000 description 11
- 238000005755 formation reaction Methods 0.000 description 11
- 239000003973 paint Substances 0.000 description 11
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- 238000005507 spraying Methods 0.000 description 9
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- 239000013543 active substance Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 6
- JDCQOLCSICKYGL-UHFFFAOYSA-N C1(=CC=CC=C1)P1(C=CCC1)=O.CC1(CC(C(=O)O)=CC=C1)C(=O)O Chemical class C1(=CC=CC=C1)P1(C=CCC1)=O.CC1(CC(C(=O)O)=CC=C1)C(=O)O JDCQOLCSICKYGL-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000004088 foaming agent Substances 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 150000002240 furans Chemical class 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229920002396 Polyurea Polymers 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000001414 amino alcohols Chemical class 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000006253 efflorescence Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
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- 230000006872 improvement Effects 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 3
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- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 101001033697 Homo sapiens Interphotoreceptor matrix proteoglycan 2 Proteins 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 102100039092 Interphotoreceptor matrix proteoglycan 2 Human genes 0.000 description 2
- ZBVOEVQTNYNNMY-UHFFFAOYSA-N O=P1=CCCC1 Chemical class O=P1=CCCC1 ZBVOEVQTNYNNMY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
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- 239000005864 Sulphur Substances 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
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- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
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- 206010000269 abscess Diseases 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
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- 238000001879 gelation Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229910052736 halogen Chemical group 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005305 interferometry Methods 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- FJDXCVIYXHYGON-UHFFFAOYSA-N n'-(2,6-diethylphenyl)methanediimine Chemical compound CCC1=CC=CC(CC)=C1N=C=N FJDXCVIYXHYGON-UHFFFAOYSA-N 0.000 description 1
- VTSXWGUXOIAASL-UHFFFAOYSA-N n'-tert-butyl-n-methylmethanediimine Chemical compound CN=C=NC(C)(C)C VTSXWGUXOIAASL-UHFFFAOYSA-N 0.000 description 1
- JCNCSCMYYGONLU-UHFFFAOYSA-N n,n'-bis(2-methylphenyl)methanediimine Chemical compound CC1=CC=CC=C1N=C=NC1=CC=CC=C1C JCNCSCMYYGONLU-UHFFFAOYSA-N 0.000 description 1
- ZWQISDZDMLUMQW-UHFFFAOYSA-N n-(2-ethylcyclohexyl)-n'-(2-propan-2-ylphenyl)methanediimine Chemical compound CCC1CCCCC1N=C=NC1=CC=CC=C1C(C)C ZWQISDZDMLUMQW-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
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- 229920001778 nylon Polymers 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
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- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 238000011084 recovery Methods 0.000 description 1
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- 238000012216 screening Methods 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
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- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
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- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical group NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
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- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
- C09K8/805—Coated proppants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Laminated Bodies (AREA)
Abstract
A proppant comprises a particle and a polycarbodiimide coating disposed on the particle. The polycarbodiimide coating comprises the reaction product of a polymeric isocyanate and a monomeric isocyanate, in the presence of a catalyst. A method of forming the proppant comprises the steps of providing the particle, providing the polymeric isocyanate, providing the monomeric isocyanate, providing the catalyst, reacting the polymeric isocyanate and the monomeric isocyanate in the presence of the catalyst to form the polycarbodiimide coating, and coating the particle with the polycarbodiimide coating.
Description
Related application
The application requires respectively on October 29th, 2008 and the U.S. Provisional Patent Application 61/109,226 of submission on July 28th, 2009 and 61/229,093 right of priority and all authority thereof, and its disclosure is all incorporated the present invention into by reference at this.
Invention field
The present invention relates generally to a kind of propping agent (proppant) and form the method for this propping agent.More specifically, the propping agent that the present invention relates to comprise particle He place the coating on the described particle, it uses in the hydraulic fracture process on stratum.
Background technology
The domestic energy demand of the U.S. has surpassed the obtainable energy at present, and it is forced to increase to foreign oil fuel such as the gentle dependence of oil.Simultaneously, what existing american energy was serious underuses, and part is as not exquisite oil-fired downgrade owing to the gentle reoovery method of inefficient oil and raw material.
Oil fuel is exploited from underground conservation pool via well bore usually.Oil fuel at present by the hydraulic fracture stratum as rock piece and from the low-permeability water reservoir, exploit with porosity and rate of permeation in various degree.Hydraulic fracture improves output by producing the broken face of dispersing from underground conservation pool or well bore, and the flow passage of increase is provided for oil fuel.In the hydraulic fracture process, the carrier fluid of particular design pumps in the underground conservation pool to cause the stratum splitting with high pressure and high speed.Propping agent is mixed with carrier fluid to keep broken face to open when hydraulic fracture is finished.Propping agent comprises particle and the coating that places on the particle usually.In case remove high pressure, propping agent is retained in the broken face position, flows in the well bore to increase oil fuel thereby strut broken face.Therefore, propping agent increases oil-fired exploitation by hypertonicity, the support passage that the generation oil fuel can flow through.
Yet many existing propping agents are used at high temperature and high pressure and are higher than 70 and pressure as temperature, and promptly closure stress is higher than 7, demonstrates insufficient thermostability in the well bore of 500psi and the underground conservation pool.That is, many existing propping agents comprise coating such as epoxide or phenols coating, and it ruptures in uncontrollable mode when being exposed to this high temperature and high pressure or cuts off particle.And many existing propping agents do not comprise promoting agent such as microorganism and catalyzer, to improve the oil-fired quality that reclaims from underground conservation pool.
In addition, many existing propping agents comprise the coating with not enough resistance to crushing.That is, many existing propping agents comprise the non-homogeneous coating that contains defectiveness such as breach or depression, and this defective causes the coating early fracture and/or breaks.Because coating is generally that propping agent provides buffering effect and around the propping agent uniformly distributing high pressure, coating early fracture and/or break and can destroy the resistance to crushing of propping agent.The propping agent of crushing can not effectively strut broken face and cause the impurity of dust form in the not exquisite oil fuel usually.
In addition, many existing propping agents also demonstrate the consolidation form that can not expect and in well bore the perviousness deficiency, promptly propping agent allows oil fuel mobile degree.That is, many existing propping agents have low-permeability and hinder oil fuel to flow.In addition, many existing propping agents are consolidated into accumulative, nearly solid impenetrability propping agent bag and hinder oil fuel fully to flow and exploitation from underground conservation pool.
And, many existing propping agents be lower than approximately 3 80 ℃ of following viscosity, the low viscosity carrier fluid of 000cps is incompatible.The low viscosity carrier fluid pumps under the pressure that is higher than the high viscosity carrier fluid in the well bore usually to guarantee the suitable splitting on stratum.As a result, many existing coating are mechanically defective when being exposed to high pressure, promptly cut off particle, or with low viscosity carrier fluid chemical reaction and degraded.
At last, many existing propping agents production cost of applying via uneconomic coating method and therefore causing increasing.That is, many existing propping agents require layered coating, and it causes time-consuming and expensive coating method.
Because existing propping agent is incompatible, still has an opportunity to provide improved propping agent.
Summary of the invention and beneficial effect
The invention provides the propping agent that is used for the hydraulic fracture stratum.Propping agent comprises particle and the coating that places on the described particle, is generally poly-carbodiimide coating.The present invention also provides and forms the method that comprises particle and place the propping agent of the poly-carbodiimide coating on the described particle.Present method comprises provides particle, poly-carbodiimide coating is provided and apply described particulate step with poly-carbodiimide coating.The method on hydraulic fracture stratum also is provided.
Advantageously, propping agent of the present invention has improved the performance of the propping agent that exists.The performance of propping agent is owing to poly-carbodiimide coating.In addition, propping agent of the present invention needs few resources ground effectively to form.
Description of drawings
When considering in conjunction with appended accompanying drawing, by the following detailed description of reference, other advantage of the present invention will be apparent, become better understood simultaneously, wherein:
Fig. 1 for set forth monomeric diisocyanate (
M) and polymeric isocyanate (
The figure of the chemical constitution of various mixtures M20).
Detailed Description Of The Invention
The present invention includes propping agent, form or prepare method, the method on hydraulic fracture stratum and the method for filtered fluid of propping agent.Propping agent is used in combination with carrier fluid usually, is used for the stratum that hydraulic fracture is defined as underground conservation pool (for example well bore or water reservoir itself).Here, after hydraulic fracture, propping agent struts the broken face in the stratum.In one embodiment, propping agent can also be used for filtering the unpurified oil fuel of broken face such as crude oil to improve the raw materials quality of refinery.Yet, should understand propping agent of the present invention and can also have the application outside filtering of hydraulic fracture and crude oil, include but not limited to water filtration and artificial grass (artificial turf).
Propping agent comprises particle and the coating that places on the described particle.Coating is described hereinafter in addition.Although particle can be virtually any size, particle has the 10-100 order usually, and more generally 20-70 purpose size-grade distribution is used the commercial measurement of U.S. sieve system (United States Sieve Series) according to the canonical measure size.That is, particle has 149-2 usually, 000 μ m, the more generally granularity of 210-841 μ m.Particle with this granularity makes and uses less coating, makes coating to be applied on the particle than low viscosity, makes coating place on the described particle with homogeneity and the integrity of comparing raising with the particle with other granularity.
Although coating of particles is inessential, compare with particle with other shape, have viscosity that the spheric particle makes the hydraulic fracture composition usually increase less, as statement in more detail hereinafter.The hydraulic fracture composition is the mixture that comprises carrier fluid and propping agent.Usually, particle is circle or almost spherical.
Particle contains based on 100 weight part particles usually for less than the moisture of 1 weight part.Contain greater than the technology of the common interferometry size of the particle of 1 weight part moisture and hinder particulate evenly to apply.
The particle that is suitable for the object of the invention is included in any known particle that uses in hydraulic fracture, water filtration or the artificial grass preparation process.The limiting examples of suitable particles comprises mineral, ceramic charcoal, mica, sawdust, wood chip, resin particle, polymer beads and combination thereof as sintered ceramic particle, sand, nutshell, gravel, mill tailings, coal ash, rock, smelting, diatomite, crushing.
Sand is preferred particle, and when being applied to this technology, sand is commonly referred to as the sand of splitting.The example of suitable sand includes but not limited to Arizona sand, Wisconsin sand, Brady sand and Ottawa sand.Other particle that this paper do not enumerate should be understood and also the object of the invention may be suitable for.Based on cost and practicality, for not needing filtering application, inorganic materials is normally favourable as sand and sintered ceramic particle.
The specific examples that is suitable as particulate sand of the present invention is an Arizona sand.Arizona sand is by BASF Corporation of Florham Park, and New Jersey is commercially available.Arizona sand is atmospheric disintegration of rocks and the natural particle of corrosive that comes from preexist.This sand is usually coarse and be roughly spheric.Other sand that is suitable for the object of the invention is Ottawa sand, and by U.S.Silica Company of Berkeley Springs, WV is commercially available.Being applied to particularly preferred Arizona sand of the present invention is size 20/40 Arizona sand, and particularly preferred Ottawa sand is size 40/70Ottawa sand.
The specific examples of suitable sintered ceramic particle includes but not limited to aluminum oxide, silica, bauxite and combination thereof.Sintered ceramic particle can also comprise the tackiness agent of similar clay.
Promoting agent also can be included in the particle.For the present invention, suitable promoting agent includes but not limited to organic compound, microorganism and catalyzer.The specific examples of microorganism includes but not limited to anaerobion, aerobic microorganism and combination thereof.The microorganism that is suitable for the object of the invention is by LUCA Technologies of Golden, and Colorado is commercially available.The specific examples of suitable catalyst comprises FCC catalysts, hydrotreating catalyst and combination thereof.Usually select FCC catalysts to be used to require by the petroleum gas of crude oil preparation and/or the application of gasoline.Usually select hydrotreating catalyst be used to require by the gasoline of crude oil preparation and/application of kerosene.Will also be understood that other catalyzer that this paper does not state, organic or inorganic also may be suitable for the object of the invention.
For requiring filtering application, this other promoting agent is normally favourable.As an example, sand and sintered ceramic particle are usually as the particle that supports or strut the broken face in the stratum that is defined as the underground storage layer, and as promoting agent, microorganism and catalyzer are generally used for removing impurity from crude oil or water.Therefore, sand/sintered ceramic particle is particularly preferred with combination as the microorganism/catalyzer of promoting agent for crude oil or water filtration.
Be suitable for the object of the invention particle in addition can be by resin and polymer formation.The specific examples that is used for described particulate resin and polymkeric substance includes but not limited to urethane, poly-carbodiimide, polyureas, polyacrylate(s), Polyvinylpyrolidone (PVP), acrylonitrile-butadiene vinylbenzene, polystyrene, polyvinyl chloride, fluoroplastics, polysulphide, nylon and combination thereof.
As indicated above, propping agent also comprises coating.Service temperature and pressure in usually relative stratum of coating and/or the underground conservation pool provide protection for particle.In addition, coating protects particle to prevent the seal-off pressure that the stratum applies usually.The also relative envrionment conditions protection of coating particle, and particulate division and/or efflorescence are minimized.In some embodiments, coating also provides ideal reactivity and/or filtration capacity for propping agent.As mentioned before, coating places on the particle.As used herein, term " place ... on " comprise " configuration " particle and particle is partially or completely covered with coating.
Coating is selected from polyurethane coating, carbamide paint, poly-carbodiimide coating, carboxaldehyde radicals coating and combination thereof usually.Preferably, coating is poly-carbodiimide coating.Yet, should understand other coating that this paper do not state and also may be suitable for the object of the invention.Usually select coating based on the desired properties of propping agent and the operational condition of expectation.
In one embodiment, coating is polyurethane coating.Usually select polyurethane coating to be used for the application of lower temperature and pressure, for example need temperature to be lower than 123 ℃ and pressure and be lower than 7, the application of 500psi.Based on cost, to select to compare with other coating, polyurethane coating also is favourable usually.
Polyurethane coating comprises the reaction product of isocyanate component and isocyanate-reactive component.Suitable isocyanate component comprises any isocyanic ester known in the art.Yet isocyanate component is selected from MDI, tolylene diisocyanate (TDI) and the combination thereof of monomer diphenylmethanediisocyanate (MMDI), polymkeric substance MDI (pMDI), carbodiimide modified usually.Those skilled in the art select isocyanate component based on economy and stability usually.For example, pMDI provides high crosslink density and medium-viscosity usually.Perhaps, MMDI and TDI provide low viscosity and high NCO content usually, have low nominal functionality.Isocyanate component is by BASF Corporation of Florham Park, and New Jersey is with trade(brand)name
Commercially available.
The viscosity of isocyanate component under 25 ℃ is generally 1-3, and 000, be more typically 20-700, be generally 50-300cps most, make thorough mixing, and make isocyanate component be applied on the particle by for example spraying ideally.In addition, isocyanate component has 1-5 usually, 1.5-4 more generally, and the nominal functionality of the most common 2.0-2.7 makes isocyanate component and isocyanate-reactive component effecting reaction.Usually, the NCO content of isocyanate component is 20-50%, is more typically 25-40%, is generally 30-33% most, with excellent molecule crosslinked density that isocyanate component is provided to help to form polyurethane coating.Above-mentioned NCO content also provides optimized chemical bond/unit mass to improve cost efficiency for isocyanate component.
The isocyanate-reactive component can comprise polyamines, but more generally comprises polyvalent alcohol.In one embodiment, polyol derivative is from dipropylene glycol initiator.In another embodiment, polyol derivative is from the ah aromatic amihe-based initiator and comprise the alkylene oxide substituting group.For described substituting group, the example of suitable alkylene oxide includes but not limited to ethylene oxide, propylene oxide, oxybutylene, oxidation amylene, alkylene oxide-tetrahydrofuran compound, epihalohydrin and inferior ha styt-ehe and combination thereof.The example that is suitable for ah aromatic amihe-based initiator of the present invention includes but not limited to have the compound of following general formula:
R wherein
1Comprise a kind of in alkyl, amido and the hydrogen, R
2-R
6Comprise a kind of in amido and the hydrogen independently of one another, as long as R
1-R
6In at least a be amido.As described herein, term " amido " refers to R-N-H and NH
2Therefore, should understand R
1Can in alkyl, amido or the hydrogen any, perhaps comprise any compound of its combination.Will also be understood that R
2-R
6Not to comprise amido or hydrogen identical and separately.
Initiator based on aromatic amine can comprise the tolylene diamine of representing by following structure:
Be tolylene diamine, include but not limited to 2,3-tolylene diamine, 2,4-tolylene diamine, 2,5-tolylene diamine, 2,6-tolylene diamine, 3,4-tolylene diamine, 3,5-tolylene diamine and composition thereof.
The viscosity of polyvalent alcohol under 25 ℃ is generally 50-20, and 000, be more typically 5,000-17,000, be generally 10 most, 000-15,000cps is sprayed on the particle to allow polyvalent alcohol.Polyvalent alcohol can be stored under 60-80 temperature and heat.Polyvalent alcohol also has 1-7 usually, 2-6 more generally, and the nominal functionality of the most common 2-4 is to allow polyvalent alcohol and isocyanate component effecting reaction and to reduce the cost of polyvalent alcohol.Usually, the OH value of polyvalent alcohol is 15-1000, is more typically 300-600, even is more typically 350-500, is generally 380-450 most, so that the maximization of the cross-linking density of polyurethane coating.
Particularly in one embodiment, polyvalent alcohol is the polyether glycol that amine causes.In another embodiment, polyvalent alcohol is the polyether glycol that trifunctional alcohol causes.Will also be understood that the isocyanate-reactive component can comprise more than a kind of polyvalent alcohol.Suitable polyvalent alcohol is by BASF Corporation of Florham Park, and New Jersey is with trade(brand)name
Commercially available.
The isocyanate-reactive component also can comprise linking agent.Linking agent is connected polymer chain in the polyurethane coating usually.Therefore, linking agent is present in the isocyanate-reactive component usually to improve hardness and to reduce the contraction of polyurethane coating.The hydroxyl value of linking agent is generally 800-1,200mg KOH/g.Suitable crosslinking agent comprises any linking agent as known in the art, for example glycol ether in the water and diethanolamine.
The isocyanate-reactive component can comprise binder component in addition.Suitable binder component includes but not limited to tensio-active agent, whipping agent, end-capping reagent, dyestuff, pigment, thinner, solvent, features additive such as oxidation inhibitor, ultra-violet stabilizer, biocides, adhesion promotor, static inhibitor, fire retardant, spices and combination thereof.For example pigment allows coating visual assessment thickness and integrity and the various market advantages can be provided.And pneumatogen and chemical foaming agent are selected from the polyurethane coating that requires foaming usually.That is, in one embodiment, coating can comprise the foamed coating that places on the particle.And, should understand term " place ... on " comprise by coating (in this example for foamed coating) part and cover fully.Foamed coating is generally used for requiring the application that contacts that improves between propping agent and the crude oil.That is, foamed coating limits the microchannel usually and increases the surface-area that contacts between crude oil and catalyzer and/or the microorganism.Foamed coating is selected from foamed polyurethane coating, polyureas foamed coating and combination thereof usually.In one embodiment, placing the coating on the particle is foamed polyurethane coating.
Tensio-active agent exists as binder component usually or exists in binder component, is used for comprising the application of foamed polyurethane coating.In this embodiment, there be the miscibility of tensio-active agent usually with the stability and the improvement component of control cellularstructure and improvement foamed polyurethane coating.Suitable tensio-active agent comprises any tensio-active agent known in the art, as polysiloxane and nonyl phenol ethoxylate.Usually, tensio-active agent is the polysiloxane of selecting according to the reactivity of polyvalent alcohol.
Whipping agent is present in the binder component of isocyanate-reactive component usually to help the formation of foamed polyurethane coating.That is, as known in the art, in the polyurethane foam reaction process between isocyanate component and isocyanate-reactive component, whipping agent promotes the release of foamed gas, and it forms abscess space (cell void) in foamed polyurethane coating.Whipping agent can be pneumatogen or chemical foaming agent.
Term " pneumatogen " refers to not the whipping agent that foamed gas is provided with isocyanate component and/or the reaction of isocyanate-reactive component chemical.Pneumatogen can be gas or liquid.The liquid pneumatogen is evaporated to gas usually and becomes liquid usually again when cooling when heating.Pneumatogen reduces the thermal conductivity of foamed polyurethane coating usually.The pneumatogen that is suitable for the object of the invention can comprise hydrogen fluorine carbon (HFC), hydrocarbon and combination thereof.The ozone depletion potential of most typical pneumatogen is generally 0.
Term " chemical foaming agent " refers to the whipping agent that foams with release gas with isocyanate component or the reaction of other component chemical.The example that is suitable for the chemical foaming agent of the object of the invention comprises formic acid, water and combination thereof.The specific examples that is suitable for the whipping agent of the object of the invention is a water.
The binder component of isocyanate-reactive component can also comprise end-capping reagent.End-capping reagent is present in the binder component usually to postpone the set time of cream time and increase foamed polyurethane coating.Suitable end-capping reagent is selected according to the reactivity of isocyanate component usually.Usually, end-capping reagent is a polymeric acid, promptly has the polymkeric substance of repeating unit and a plurality of acid functional groups.
The isocyanate-reactive component comprises catalyst component usually in addition.Catalyst component is present in usually in the isocyanate-reactive component and reacts with the polyurethane foam between catalysis isocyanate component and the isocyanate-reactive component.Should understand in the polyurethane foam reaction between isocyanate component and isocyanate-reactive component usually not spent catalyst component.That is, catalyst component participates in the flexibel polyurethane foamable reaction usually, but does not consume.Catalyst component can comprise any appropriate catalyst known in the art or mixture of catalysts.The example of appropriate catalyst includes but not limited to gelation catalyst, for example the crystalline catalysts in the dipropylene glycol; Kicker, for example two (dimethyl aminoethyl) ethers in the dipropylene glycol; And tin catalyst, for example stannous octoate.
In another embodiment, coating is carbamide paint.Usually select carbamide paint to be used for the application of comparatively high temps and pressure, for example be exposed to the temperature that is higher than 123 ℃ and be higher than 7 when propping agent, during the pressure of 500psi.
Carbamide paint comprises the reaction product of isocyanate component and amine.Amine can comprise any amine known in the art.Amine generally includes but is not limited to primary amine and secondary amine, aliphatic series and/or cycloaliphatic amines.Amine can comprise any other functional group known in the art, includes but not limited to hydroxyl, thiol group, alkyl, cyclic group, aromatic group and combination thereof.Amine should be understood and acid amides can also be comprised.If amine comprises acid amides, acid amides can be an any kind known in the art.Acid amides generally includes but the polyesteramide that is not limited to be obtained by unsaturated or saturated carboxylic acid or acid anhydride, multifunctional unsaturated or saturated amino alcohol and combination of polymers thereof.In all embodiments of the present invention, expectation can be used any amine known in the art or acid amides.
The specific examples of suitable amine includes but not limited to diethyl toluene diamine; Aromatic diamine such as N, N '-two (1-methyl-propyl)-1,4-phenylenediamine and 4,4 '-two (sec-butylamine) ditan; Polyether diamine; Quadrol; Isophorone diamine; The methane diamines as 4,4 '-dicyclohexyl methyl hydride diamines and 4,4 '-Dimethylcyclohexyl methane diamines; Amino-terminated polyoxypropylene glycol; With amino-terminated glycerine propoxylated glycerine.
Should understand the reaction product that carbamide paint can also comprise isocyanate component, amine and above-mentioned binder component.For example, in one embodiment, carbamide paint is defined as the polyureas foamed coating in addition and comprises physics and/or chemical foaming agent.
In preferred embodiments, coating is poly-carbodiimide coating.Usually select poly-carbodiimide coating be used for the requirement excellence paint stability and with the adhering application of particulate.As an example, when propping agent is exposed to significant compression and/or shearing force, and the temperature in stratum and/or the underground storage layer that limited by this stratum is when surpassing 500 °F, poly-carbodiimide coating particularly suitable.Poly-carbodiimide coating in nature normally viscosity and depend on molecular weight to solid, slightly soluble or be insoluble to organic solvent usually.Any suitable poly-carbodiimide coating can be used for the object of the invention.
Usually, poly-carbodiimide coating reacts formation by the isocyanic ester ester in the presence of catalyzer.Poly-carbodiimide coating can be the reaction product of a kind isocyanate.Yet for the present invention, poly-carbodiimide coating is preferably the reaction product of at least two kinds of different isocyanic ester, makes the isocyanic ester of above introducing be defined as first isocyanic ester and second isocyanic ester that is different from first isocyanic ester.Obviously, poly-carbodiimide coating can be the reaction product of two or more isocyanic ester.
Isocyanic ester can be the isocyanic ester of the known any kind of those skilled in the art.This isocyanic ester can be for having two or more functional groups, for example the polyisocyanates of two or more NCO functional groups.The isocyanic ester that is suitable for the object of the invention includes but not limited to aliphatic series and aromatic isocyanate.In various embodiments, isocyanic ester is selected from diphenylmethanediisocyanate (MDI), polymerization diphenylmethanediisocyanate (pMDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and combination thereof.
Isocyanic ester can be isocyanate prepolymer.Isocyanate prepolymer is generally the reaction product of isocyanic ester and polyvalent alcohol and/or polyamines.Used isocyanic ester can be above-mentioned any isocyanic ester in the prepolymer.The polyvalent alcohol that is used to form prepolymer is selected from ethylene glycol, glycol ether, propylene glycol, dipropylene glycol, butyleneglycol, glycerine, TriMethylolPropane(TMP), trolamine, tetramethylolmethane, sorbyl alcohol, biological multielement alcohol and combination thereof usually.The polyamines that is used to form prepolymer is selected from quadrol, tolylene diamine, diaminodiphenyl-methane and polymethylene polyphenylene polyamines, amino alcohol and combination thereof usually.The example of suitable amino alcohol comprises thanomin, diethanolamine, trolamine and combination thereof.
Can be used to prepare the concrete isocyanic ester that gathers carbodiimide coating and include but not limited to tolylene diisocyanate; 4,4 '-diphenylmethanediisocyanate; The metaphenylene vulcabond; 1, the 5-naphthalene diisocyanate; 4-chloro-1, the 3-phenylene vulcabond; Tetramethylene diisocyanate; Hexamethylene diisocyanate; 1,4-dicyclohexyl vulcabond; 1,4-cyclohexyl diisocyanate, 2,4,6-toluene triisocyanate, 1,3-di-isopropyl phenylene-2,4-vulcabond; 1-methyl-3,5-diethyl phenylene-2,4-vulcabond; 1,3,5-triethyl phenylene-2,4-vulcabond; 1,3,5-triisopropyl phenylene-2,4-vulcabond; 3,3 '-diethyl biphenyl base-4,4 '-vulcabond; 3,5,3 ', 5 '-tetraethyl-ditan-4,4 '-vulcabond; 3,5,3 ', 5 '-tetra isopropyl ditan-4,4 '-vulcabond; 1-ethyl-4-ethoxyl phenenyl-2, the 5-vulcabond; 1,3,5-triethylbenzene-2,4,6-triisocyanate; 1-ethyl-3,5-diisopropyl benzene-2,4,6-triisocyanate and 1,3,5-triisopropylbenzene-2,4,6-triisocyanate.Other suitable poly-carbodiimide coating also can be by aromatic diisocyanate with one or two aryl, alkyl, aralkyl or alkoxy substituent (wherein at least one substituting group has at least two carbon atoms) or isocyanic ester preparation.The specific examples of suitable isocyanic ester comprises
L5120,
M,
ME,
MI,
M20 and
M70, all are by BASF Corporation of Florham Park, and NJ is commercially available.
As indicated above, multiple isocyanic ester can react and form poly-carbodiimide coating.When one or more isocyanate reactions formed poly-carbodiimide coating, physicals such as hardness, intensity, toughness, creep and the fragility of poly-carbodiimide coating can further be optimized and balance.
In particularly preferred embodiments, first isocyanic ester is further defined as polymeric isocyanate, and second isocyanic ester is further defined as monomeric diisocyanate.Equally,
M20 and
The mixture of M can react and form poly-carbodiimide coating.
M20 comprises polymeric isocyanate such as polymerization diphenylmethanediisocyanate, and comprises monomeric diisocyanate.
M only comprises monomeric diisocyanate.As known in the art, monomeric diisocyanate includes but not limited to 2, and 4 '-diphenylmethanediisocyanate (2,4 '-MDI) and 4,4 '-diphenylmethanediisocyanate (4,4 '-MDI).As known in the art, polymeric isocyanate comprises the isocyanic ester with two or more aromatic rings.Set forth among Fig. 1
M and
The various mixtures of M20.
The NCO content of M20 is about 31.5 weight %,
The NCO content of M is about 33.5 weight %.
In the mixture
The amount increase of M20 increases the amount of polymkeric substance MDI in the mixture, and the amount of polymkeric substance MDI increases the physicals of the poly-carbodiimide coating of influence in the mixture.For example, in one embodiment,
M20 and
The mixture reaction of M forms poly-carbodiimide coating.Generally speaking, in mixture, increase
The amount of M20 and reduction
The amount of M forms harder, stronger and the remarkable poly-carbodiimide coating of creep not; Yet poly-carbodiimide coating also may be brittle.Equally, in mixture, reduce
The amount of M20 and increase
The amount of M reduces the fragility of poly-carbodiimide coating usually but increases creep.
In particularly preferred embodiments, polymeric isocyanate as
M20 is usually with the about 100 weight % of about 20-, the about 80 weight % of more generally about 40-, the quantitative response of the about 70 weight % of the most common about 60-, monomeric diisocyanate as
M is usually with the about 80 weight % of about 20-, the about 60 weight % of more generally about 25-, and the quantitative response of the about 40 weight % of the most common about 30-is all based on the gross combination weight of polymeric isocyanate and monomeric diisocyanate.In another embodiment preferred, polymeric isocyanate and monomeric diisocyanate are with 4: 1-1: 4, more generally 2.5: 1-1: 1, even more generally 2.0: 1 weight ratio reaction forms poly-carbodiimide coating.
One or more isocyanic ester heat in the presence of catalyzer usually to form poly-carbodiimide coating.Catalyzer can be the catalyzer of the known any kind of those skilled in the art.Generally speaking, catalyzer is selected from phosphorus compound, teritary amide, alkaline metal cpds, carboxylic metallic salt, non-alkaline organometallic compound and combination thereof.For example, one or more isocyanic ester can add the poly-carbodiimide coating of thermosetting in the presence of phosphorus compound.The example of suitable phosphorus compound includes but not limited to that phospholene oxides (phospholene oxide) is as 3-methyl isophthalic acid-phenyl-2-phospholene oxides, 1-phenyl-2-phospholene-l-oxide compound, 3-methyl isophthalic acid-2-phospholene-l-oxide compound, 1-ethyl-2-phospholene-l-oxide compound, 3-methyl-l-phenyl-2-phospholene-l-oxide compound and its 3-phospholene isomer.The specially suitable phospholene oxides 3-methyl isophthalic acid-phenyl-2-phospholene oxides that following structure is represented of serving as reasons:
In particularly preferred embodiments, 3-methyl isophthalic acid-phenyl-2-phospholene oxides is usually with greater than about 1 to about 100PPM, and more generally about 2 to about 750PPM, and the most common about amount of 3 to about 500PPM is present in the poly-carbodiimide coating.
The concrete poly-carbodiimide coating that is suitable for the object of the invention includes but not limited to DIC, dicyclohexylcarbodiimide, the methyl tertbutyl carbodiimide, 2,6-diethyl phenyl carbodiimide, di o tolyl carbodiimide, 2,2 '-the dimethyl diphenyl carbodiimide, 2,2 '-di-isopropyl phenylbenzene carbodiimide, 2-dodecyl-2 '-n-propyl phenylbenzene carbodiimide, 2,2 '-diethoxy phenylbenzene dichloro phenylbenzene carbodiimide, 2,2 '-xylyl phenylbenzene carbodiimide, 2,2 '-dibenzyl phenylbenzene carbodiimide, 2,2 '-the dinitro diphenyl carbodiimide, 2-ethyl-2 '-isopropyl diphenyl base carbodiimide, 2,6,2 ', 6 '-tetraethyl-phenylbenzene carbodiimide, 2,6,2 ', 6 '-four sec-butyl phenylbenzene carbodiimides, 2,6,2 ', 6 '-tetraethyl--3,3 '-dichloro phenylbenzene carbodiimide, 2-ethyl cyclohexyl-2-isopropyl phenyl carbodiimide, 2,4,6,2 ', 4 ', 6 '-six isopropyl diphenyl base carbodiimides, 2,2 '-the diethyl dicyclohexylcarbodiimide, 2,6,2 ', 6 '-the tetra isopropyl dicyclohexylcarbodiimide, 2,6,2 ', 6 '-tetraethyl-dicyclohexylcarbodiimide and 2,2 '-the dichloro dicyclohexylcarbodiimide, 2,2 '-diethyl-ester group phenylbenzene carbodiimide, 2,2 '-monomer of dicyano phenylbenzene carbodiimide etc., oligopolymer and polymkeric substance.
Poly-carbodiimide coating is usually based on 100 weight part particles serving as the about 10 weight % of about 0.1-, the about 7.5 weight % of more generally about 0.5-, and the amount of the about 6.0 weight % of the most common about 1.0-is present in the propping agent.
Poly-carbodiimide coating can original position form, and wherein poly-carbodiimide coating places on the particle in the process that forms poly-carbodiimide coating.With differently described, poly-carbodiimide coating composition combines with particle usually and poly-carbodiimide coating places on the particle.
Yet in one embodiment, poly-carbodiimide coating forms also and is applied to for some time after, for example mixes with particle and is exposed to temperature above 100 ℃ with coated particle and form propping agent.Advantageously, this embodiment allows in handling chemical under the control the professional, forms poly-carbodiimide coating in the position that is designed to handle chemical.In case form, poly-carbodiimide coating can be delivered to other position, is applied to particle, and heating.Other advantage of this embodiment comprises faster sand coating cycling time, less generation CO in the particle coated process
2And the use of minimizing catalyzer.Except above-mentioned advantage, also have logic and the real advantage relevant with this embodiment.For example, be applied to particle such as splitting sand if will gather carbodiimide coating, then can after the preparation of splitting sand, apply carbodiimide coating immediately, when splitting sand at elevated temperatures the time, do not need poly-carbodiimide coating of reheat and splitting sand, thereby reduce the energy requirement that forms propping agent.
In this embodiment, isocyanic ester and catalyst mix form reaction mixture.Specially suitable isocyanic ester includes but not limited to
M20,
M and composition thereof.Specially suitable catalyzer is 3-methyl isophthalic acid-phenyl-2-phospholene oxides.With the reaction mixture heating, form poly-carbodiimide coating.The reaction times of reaction mixture is depended on the amount of catalyzer in temperature, pressure and the reaction mixture that reaction mixture keeps.Along with the carrying out in reaction times, the molecular weight and the viscosity increase of carbodiimide coating carried out and gathered in the formation of poly-carbodiimide coating.After reaction times, will be in poly-carbodiimide coating, other isocyanic ester and the mixture of catalysts cooling of the formation of molten state.This mixture solidifies at ambient temperature.Usually, poly-carbodiimide coating, isocyanic ester and the mixture of catalysts that is curing, crystalline state now is processed into various size and/or efflorescence.Poly-carbodiimide coating, isocyanic ester and the mixture of catalysts of present similar solid thermoplastics can be applied to particle.With poly-carbodiimide coating, isocyanic ester with mixture of catalysts is for example mixed with particle and be heated to time of predetermined amount and be applied to particle greater than 100 ℃ temperature and comprise the propping agent that places the poly-carbodiimide coating on the particle with formation.
As indicated above, poly-carbodiimide coating is usually by making a kind of isocyanic ester or multiple isocyanate reaction form in the presence of catalyzer.Yet should understand poly-carbodiimide coating can be formed by other reactant that is not isocyanic ester.Only as an example, the poly-carbodiimide coating of the present invention can with as the urea of reactant for example thiocarbamide form.Be suitable for forming other case description of the reactant that gathers carbodiimide in " Chemistry and Technology of Carbodiimides ", Henri Ulrich, John Wiley ﹠amp; Sons, Ltd., Chichester, West Sussex, among the England (2007), its whole disclosures are incorporated the present invention by reference into.
In another embodiment, coating is carboxaldehyde radicals coating.Usually select carboxaldehyde radicals coating to be used for the application of the excellent hardness of requirement.Carboxaldehyde radicals coating can further be selected from resole coating, the coating that contains novolac polymer, furans coating, carbamide coating, melocol coating and combination thereof.
In one embodiment, carboxaldehyde radicals coating is resole coating.Resole coating generally includes the reaction product that phenol, aldehyde and per molecule contain the aliphatic hydroxyl cpd of two or more hydroxyls.The example of suitable phenol comprises any phenol that can be used to form phenolic resin paint known in the art, comprises substituted phenol and unsubstituted phenol.Suitable substituted phenol includes but not limited to alkyl-substituted phenols, aryl substituted phenol, cycloalkyl substituted phenol, alkenyl substituted phenol, alkoxyl group substituted phenol, aryloxy substituted phenol and halogen substituted phenol.
The example that is suitable for the aldehyde of the object of the invention includes but not limited to formaldehyde, acetaldehyde, propionic aldehyde, furfural, phenyl aldehyde and formaldehyde.Suitable aldehyde contains 1-8 carbon atom usually.Usually, aldehyde is formaldehyde.
The hydroxyl value of example that per molecule contains the aliphatic hydroxyl cpd of two or more hydroxyls is 200-1,850mg KOH/g.Suitable aliphatic hydroxyl cpd comprises ethylene glycol, propylene glycol, 1, and ammediol, glycol ether, triglycol, glycerine, sorbyl alcohol and hydroxyl value are greater than about 200 polyether glycol.Usually, aliphatic hydroxyl cpd is a glycerine.
The molar excess aldehyde of every moles of phenol is generally used for preparing resole coating.The phenol of resole coating and the mol ratio of aldehyde are generally about 1: 1 to about 1: 3, are more typically about 1: 1 to about 1: 1.95.
In another embodiment, carboxaldehyde radicals coating is the coating that contains novolac polymer.The coating that contains novolac polymer generally includes phenolic compound and the reaction product of aldehyde in the presence of acid catalyst.Suitable phenolic compound comprises any above-mentioned phenol.Suitable aldehyde comprises any aldehyde known in the art, includes but not limited to formalin, paraformaldehyde, formaldehyde, acetaldehyde, furfural and phenyl aldehyde.Usually, aldehyde is formaldehyde.Suitable acid catalyst comprises strong inorganic acid such as sulfuric acid, phosphoric acid and hydrochloric acid and organic acid such as oxalic acid and tosic acid.Contain the phenol of coating of novolac polymer and the mol ratio of aldehyde and be generally about 1: 0.85 to about 1: 0.4.
In another embodiment, carboxaldehyde radicals coating is furans coating.Furans coating generally includes urea formaldehyde and furfuryl alcohol; Urea formaldehyde, phenol formaldehyde and furfuryl alcohol; Phenol formaldehyde and furfuryl alcohol; The perhaps reaction product of formaldehyde and furfuryl alcohol.Usually, furans coating comprises the reaction product of urea formaldehyde and furfuryl alcohol.
In another embodiment, carboxaldehyde radicals coating is carbamide coating.Carbamide coating generally includes the reaction product of resole and trimeric cyanamide.Suitable resole and trimeric cyanamide comprise any resole known in the art and trimeric cyanamide.
In yet another embodiment, carboxaldehyde radicals coating is melocol coating.Melocol coating comprises the reaction product of urea monomer and formaldehyde monomers.Suitable urea monomer and formaldehyde monomers comprise any urea monomer known in the art and formaldehyde monomers.Usually, urea monomer and formaldehyde monomers are with about 1.1: about 4: 1 of 1-, more generally about 2.1: 1-3.2: 1 formaldehyde and urea molar ratio reaction.
Coating can also be further defined to controllable release.That is, coating can with controllable manner dissolve methodically and/or hydrolysis particle is exposed to the oil fuel in the underground conservation pool.Coating dissolves in the mode of unanimity in the section usually at the fixed time gradually.This embodiment is particularly useful for utilizing in promoting agent such as microorganism and/or the Application of Catalyst.That is, for requiring to filter in the application of oil fuel or water the common controllable release of coating.
Any comprise with the crosslinked embodiment of isocyanate component in, for example in the embodiment that comprises polyurethane coating, poly-carbodiimide coating or carbamide paint, coating demonstrates the not wettability in the presence of water usually, measures according to standard contact angle measuring method known in the art.The contact angle of coating is usually greater than 90 ° and can be categorized as hydrophobic.As a result, the common application that partly swims in the underground conservation pool and be generally used for requiring foamed coating of the propping agent of this embodiment.
Coating of the present invention can be for crosslinked, and wherein it solidified before pumping into propping agent in the underground conservation pool, and perhaps coating can be curable, thereby coating is because inherent condition and solidifying in underground conservation pool wherein.These notions further describe hereinafter.
Propping agent of the present invention can comprise the particle of sealing with crosslinked coating.Crosslinked coating is generally propping agent and shatter strength or resistance to crushing is provided and prevents the propping agent agglomeration.Because crosslinked coating solidified before propping agent is pumped to underground conservation pool, so propping agent usually even also can not crush or agglomeration under high pressure and hot conditions.
Perhaps, propping agent of the present invention can comprise the particle of sealing with hardenable coatings.Hardenable coatings is usually in in-situ consolidation and curing.Hardenable coatings is not crosslinked before propping agent is pumped to underground conservation pool usually, promptly solidifies.The substitute is, hardenable coatings solidifies under high pressure and hot conditions in underground conservation pool usually.Comprise the particulate propping agent that is encapsulated with hardenable coatings and be generally used for high pressure and hot conditions.
In addition, but comprise the particulate propping agent that is encapsulated with hardenable coatings and can be categorized as curable propping agent underground solidification propping agent and can partly solidified propping agent.But the underground solidification propping agent is completely solidified in underground conservation pool usually, and can partly solidified propping agent partly solidified before pumping into underground conservation pool usually.Can partly solidified propping agent completely solidified in underground conservation pool usually then.But propping agent of the present invention can be underground solidification or can be partly solidified.
Layered coating can be applied to particle to form propping agent.Equally, propping agent of the present invention can comprise and has the particle that places the crosslinked coating on the particle and place hardenable coatings on the crosslinked coating, and vice versa.
Propping agent can further comprise siliceous adhesion promotor.This adhesion promotor is also so-called coupling agent or tackiness agent in this area.Adhesion promotor with adhesion of coatings on particle.More specifically, adhesion promotor has the organofunctional silane group usually to improve the adhesivity of coating on particle.Not bound by theory, think that adhesion promotor allows covalent bonding between particle and the coating.In one embodiment, by before with the coating coated particle, adhesion promotor being applied to particle and activating particle surface with adhesion promotor.In this embodiment, adhesion promotor can be applied to particle by the various technology that apply, and includes but not limited to spraying, impregnated with particles is medium at coating.In another embodiment, adhesion promotor can be introduced in the coating.Equally, when coating was applied to particle, particle was exposed to adhesion promotor then simply.Adhesion promotor is used for the application of requirement coating and particulate excellent adhesion, and for example wherein propping agent is subjected to the application of shear action in aqueous environment.The use of adhesion promotor provides coating and particulate adhesivity, even make propping agent, comprises coating, particle or both, because when closure stress and splitting, coating still sticks to particle surface.
The example of suitable siliceous adhesion promotor includes but not limited to glycidoxy-propyltrimethoxy silane, the aminoethylamino propyl trimethoxy silicane, methyl allyl acyloxypropyl trimethoxysilane, γ-An Jibingjisanyiyangjiguiwan, vinyl benzyl aminoethylamino propyl trimethoxy silicane, the epoxypropoxy methyldiethoxysilane, r-chloropropyl trimethoxyl silane, phenyltrimethoxysila,e, vinyltriethoxysilane, tetraethoxysilane, methyl dimethoxysilane, two-triethoxysilylpropyltetrasulfide two polysulfur silanes, two-triethoxysilylpropyltetrasulfide four polysulfur silanes, phenyl triethoxysilane, aminosilane and combination thereof.
The specific examples of suitable adhesion promotor includes but not limited to Silquest
TMA1100, Silquest
TMA1110, Silquest
TMA1120, Silquest
TM1130, Silquest
TMA1170, Silquest
TMA-189 and Silquest
TMY9669, all can be by Momentive Performance Materials of Albany, and NY is commercially available.Specially suitable siliceous wetting agent is Silquest
TMA1100, i.e. γ-An Jibingjisanyiyangjiguiwan.Siliceous wetting agent can be to be about 0.001 to about 10 weight % based on the poly-carbodiimide coating of 100 weight parts, and about 0.01 to about 7.5 weight % usually, and more generally about 0.1 amount to about 5 weight % is present in the propping agent.
Coating of the present invention can also comprise above about the described promoting agent of particle.In other words, promoting agent can be independent of particle and be included in the coating.Again, suitable promoting agent includes but not limited to organic compound, microorganism and catalyzer.Coating can comprise other additive, promoting agent or other material such as wetting agent, tensio-active agent etc.
Propping agent of the present invention shows excellent thermostability usually in high temperature and high pressure is used, for example be higher than 100 ℃, usually above 250 ℃, more generally be higher than 350 ℃, even more generally be higher than 500 ℃ temperature, and/or be higher than 7,500psi, usually above 10,000psi more generally is higher than 12,500psi, even more generally be higher than 15, the pressure of 000psi (being independent of said temperature).Propping agent of the present invention can be broken by coating owing to shearing or degrading when being exposed to this temperature and pressure fully.
In addition, owing to have coating of the present invention, propping agent demonstrates excellent shatter strength, also so-called resistance to crushing usually.Because this shatter strength, the coating of propping agent evenly and does not basically have defective, and as breach or depression, it causes the coating early fracture usually and/or breaks.Particularly, the shatter strength that propping agent demonstrates is 15% or maximum particulate still less, according to the pressure of American Petroleum Institute (API) RP60 at 7500-15000psi, comprise 7500,10000,12500 and the concrete stress pressure of 15000psi under measure.When using 20/40Arizona sand as particle, the preferred shatter strength of propping agent of the present invention is 10% or still less, more preferably 5% or maximum particulate still less, measure under above-mentioned identical stress pressure scope and concrete stress pressure according to API RP60.When using 40/70Ottawa sand as particle, the preferred shatter strength of propping agent of the present invention is 8% or still less, more preferably 5% or maximum particulate still less, measure under above-mentioned identical stress pressure scope and concrete stress pressure according to API RP60.The most common shatter strength of this propping agent is 2% or maximum particulate still less, measures under 8000psi and 10000psi according to API RP60.Coating of the present invention is generally propping agent and buffering effect is provided and distributes high pressure, for example closure stress equably around propping agent.Therefore, propping agent of the present invention effectively struts broken face, and makes the undesired impurity of dust granules form in the turpentole fuel not minimized.
Although can select customization according to carrier fluid, the proportion of propping agent is generally 0.1-3.0, is more typically 1.0-2.0.Those skilled in the art usually according to the proportion of carrier fluid and whether wish propping agent be light-weight or in selected carrier fluid the neutral basically floating proportion of selecting propping agent.Particularly, the proportion of wishing propping agent less than the proportion of carrier fluid so that proppants settle down in carrier fluid, minimize.In addition, based on the not wettability of the coating that comprises above-mentioned isocyanate crosslinking, the propping agent of this embodiment has 2.0-3.0, more generally 2.3-2.7g/cm usually
3Apparent density, promptly the quality of unit volume body propping agent is also referred to as tap density, according to API Recommended Practices RP60 test propping agent.The not wettability of believing coating has help support floating, depends on the selection of carrier fluid in the well bore.
In addition, propping agent makes unpredictable fixed minimizing usually.That is, propping agent is only fixed according to the selection of carrier fluid and service temperature and pressure with the ideal style of precognition, if fixed.And, propping agent usually and viscosity under 80 ℃ less than about 3, the low viscosity carrier fluid of 000cps is compatible, and when being exposed to carrier fluid and high pressure, usually basically can mechanical disruption and/or chemical degradation.At last, propping agent applies by economic coating method usually, and does not require a plurality of coating usually, therefore production cost is minimized.
As indicated above, the present invention also provides the method that forms or prepare propping agent.For this method, particle and coating are provided, preferably poly-carbodiimide coating, particle coated has poly-carbodiimide coating.Step with poly-carbodiimide coating coated particle is described hereinafter in addition.
For poly-carbodiimide coating is provided, isocyanic ester is reacted usually in the presence of catalyzer.Make isocyanate reaction form poly-carbodiimide coating.Described in some embodiment hereinafter, isocyanic ester can react before the practical coating particle and form poly-carbodiimide coating; Perhaps, isocyanic ester can react simultaneously at the practical coating particulate and form poly-carbodiimide coating.
As can using all other components in the methods of the invention (for example particle), isocyanic ester and catalyzer are described about poly-carbodiimide coating as mentioned.Isocyanic ester is preferably the reaction product of above-mentioned first and second isocyanic ester, and wherein first and second isocyanic ester preferably further are defined as polymeric isocyanate and monomeric diisocyanate respectively.In addition, as indicated above, preferred polymeric isocyanic ester and monomeric diisocyanate are with 4: 1-1: 4, more generally 2.5: 1-1: 1, even more generally 2.0: 1 weight ratio reaction to form poly-carbodiimide coating.
With poly-carbodiimide coating coated particle to form propping agent.To gather carbodiimide coating and be applied to particle with coated particle.Particle can be before with the step of poly-carbodiimide coating coated particle or simultaneously optionally heating to the temperature that is higher than 150 ℃.The preferred range of heated particle is 150-180 ℃.Heated particle makes the particulate temperature more can react the temperature that forms poly-carbodiimide coating near component.
Various technology can be used for poly-carbodiimide coating coated particle.These technology include but not limited to mix, coil coating, fluidized-bed coating, coextrusion, spraying, original position forms coating and rotating disc type is sealed.Select to apply coating according to cost, production efficiency and batch weight to the particulate technology.
In the method, isocyanic ester in the presence of catalyzer, react the step that forms poly-carbodiimide coating and with the step of gathering carbodiimide coating coated particle at 20 minutes or shorter, common 10 minutes or shorter, more generally 6 minutes or shorter, even more generally carry out jointly in time of 3-5 minute.
In case apply, can heat propping agent with further crosslinked poly-carbodiimide coating.The heating propping agent is during with further crosslinked poly-carbodiimide coating, make isocyanate reaction form the step of poly-carbodiimide coating, with the step of poly-carbodiimide coating coated particle and heating propping agent with the step of further crosslinked poly-carbodiimide coating at 30 minutes or shorter, common 20 minutes or shorter, more generally 10 minutes or shorter, even more generally carry out jointly in 6 minutes or shorter time.
In one embodiment, by in container such as reactor, mixing coating is placed on the particle.Particularly, each component such as isocyanic ester, particle and the optional catalyst with coating adds in the container to form reaction mixture.Each component can be to equate or the adding of unequal weight ratio.Usually the agitation speed that matches with the viscosity with each component is stirred reaction mixture.In addition, common reacting by heating mixture under the temperature that matches with paint-on technique and batch weight.For example, each component of coating is heated to about 130 ℃ from about 70 ℃ usually in 10 minutes or shorter time, depend on batch weight.Should understand hybrid technology can comprise each component is added in the container continuously or simultaneously.And each component can add in the container with the various timed intervals and/or temperature.
In another embodiment, coating is placed on the particle by spraying.Particularly, each component of coating contacts in spraying equipment to form coating compound.Then coating compound is sprayed on the particle to form propping agent.With paint spray cause to the particle evenly, the flawless coating of complete sum places on the particle.For example, coating is normally smooth and unbroken.Coating also has enough thickness and acceptable integrity degree usually, and it allows to require the application of controllable release propping agent in broken face.Compare with other technology, spraying also causes thinner with more consistent coating to place on the particle usually, so propping agent applies economically.Spraying granule even permission continuous production processes.Those skilled in the art select vapo(u)rizing temperature according to paint-on technique and environmental damp condition usually.All right heated particle is so that paint solidification.In addition, those skilled in the art are usually with the viscosity that matches with each component viscosity each component of spraying.
In another embodiment, the coating original position is placed on the particle, promptly in comprising coating composition and particulate reaction mixture.In this embodiment, coating is when coating places on the particle and form or part forms.Original position coating forms step and generally includes each component that coating is provided, and particle is provided, and makes each component and the particle combination of coating, and coating is placed on the particle.Original position coating forms usually by allowing to reduce production costs with processing step that the existing method that forms propping agent is compared still less.
The propping agent that forms is stored in on-the-spot external position usually according to method for preparing and before pumping into stratum and underground conservation pool.Equally, spraying is carried out outside stratum and underground conservation pool usually.Yet, be to be understood that propping agent can also just prepare before pumping into stratum and underground conservation pool.In this scheme, propping agent can prepare with portable coating unit at the scene of stratum and underground conservation pool.
The hydraulic fracture that propping agent is used for the stratum is to improve the recovery of oil etc.In common hydraulic fracture operation, prepare the hydraulic fracture composition, promptly comprise the mixture of carrier fluid, propping agent and optional various other components.Carrier fluid select according to the boring well condition and with mixed with proppants to form mixture, it is the hydraulic fracture composition.Carrier fluid can be various fluids, includes but not limited to kerosene and water.Usually, carrier fluid is a water.Various other components that can add in the mixture include but not limited to known other component of guar gum, polysaccharide and those skilled in the art.
Mixture is pumped in the underground conservation pool, and it can be a well bore, causes the stratum splitting.More specifically, apply hydraulic pressure under pressure, the hydraulic fracture composition is introduced in the underground conservation pool with the broken face in generation or the expansion stratum.When discharging hydraulic pressure, propping agent keeps broken face to open, thereby improves broken face is extracted into oil fuel or other fluid boring well from underground conservation pool ability.
For the method for filtered fluid, propping agent of the present invention provides according to the method for above-mentioned formation propping agent.In one embodiment, fluid can be turpentole etc. not.Yet should understand other fluid that the inventive method can comprise that filtration this paper does not specifically enumerate, for example air, water or Sweet natural gas.
For filtered fluid, contain turpentole not and identify by known method in the oily extraction field as the underground conservation pool median cleavage plane that does not filter crude oil.Turpentole is not exploited via underground conservation pool such as well bore usually, and as raw material provide to refinery to produce purified product such as petroleum gas, petroleum naphtha, gasoline, kerosene, gas oil, lubricating oil, heavy gas and coke.Yet the crude oil that occupy in the underground conservation pool comprises impurity such as sulphur, undesirable metal ion, tar and high-molecular-weight hydrocarbons.This impurity stops up purification apparatus and also prolongs refinery's production cycle, wishes to reduce this impurity and is out of order to prevent purification apparatus, makes purification apparatus be used to safeguard and stop time of cleaning minimizes, and makes the maximizing efficiency of process for refining.Therefore, need to filter.
For filter method, the hydraulic fracture composition is pumped in the underground conservation pool, make the hydraulic fracture composition with do not filter crude oil and contact.Usually so that in the stratum, form the speed and the pressure of one or more broken faces the hydraulic fracture composition is pumped in the underground conservation pool.Stratum median cleavage plane pressure inside can be greater than 5,000, greater than 7,000, or even greater than 10, temperature is usually above 70 °F and can depend on specific stratum and/or underground conservation pool up to 375 °F in the 000psi, broken face.
Although do not require filtration, wish that especially propping agent is the controllable release propping agent.The controllable release propping agent, the hydraulic fracture composition is in broken face inside simultaneously, and propping agent coating because pressure, temperature, pH variation and/or dissolving are dissolved in the carrier fluid with controllable manner, can be put by controlled release usually.The thickness of coating and the temperature and pressure in the broken face are depended in the dissolving fully of coating, but carry out usually 1-4 hour.Should understand term " dissolving " fully is often referred to and is less than 1% coating and still places on the particle or around the particle.Controllable release permission particle postpones to be exposed to the crude oil in the broken face.In this embodiment, when particle comprised promoting agent such as microorganism or catalyzer, particle had usually and must contact to filter or to clean the reactive position of this fluidic with controllable manner with fluid such as crude oil.If implement, this controllable release provides reactive position to be exposed to crude oil gradually to prevent that active sites is saturated.Similarly, promoting agent is responsive to contact immediately with free oxygen usually.Controllable release provides promoting agent to be exposed to crude oil gradually to prevent that promoting agent is saturated by free oxygen, especially when promoting agent is microorganism or catalyzer.
For filtered fluid, the particle that is substantially free of coating contacts with fluid such as crude oil after controllable release.Should understand term and " be substantially free of " and refer to that coating dissolves fully, and as indicated above, the coating less than 1% still places on the particle or around the particle.This term can use with above-mentioned term " dissolving fully " exchange.Use therein in the embodiment of promoting agent, by contacting with fluid, particle is usually by bio-digestion impurity screening such as sulphur, undesired metal ion, tar and high-molecular-weight hydrocarbons from crude oil.As indicated above, the combination of sand/sintered ceramic particle and microorganism/catalyzer is used in particular for filtering crude oil enough support/supports to be provided and to filter, and promptly removes impurity.So propping agent postpones particle to be exposed to by permission usually, and crude oil filters crude oil in the broken face.
Usually from underground conservation pool, extract filtering crude oil by known method in the oily extraction field via a broken face in the stratum or a plurality of broken face.Filtering crude oil provides to the olein refinery usually as raw material, and particle usually remains in the broken face.
Perhaps, in the broken face near end of life, for example contain in the broken face of the crude oil that can not extract economically by present oily extracting method, particle also can be used for extracting Sweet natural gas as fluid from this broken face.Particle particularly wherein uses the particle of promoting agent, contacts with fluid the hydrocarbon in the fluid is converted into propane or methane digests hydrocarbon by the reactive position that makes particle and/or promoting agent.Then usually by broken face results propane or the methane of known method in the Sweet natural gas extraction field from underground conservation pool.
Embodiment
The embodiment that below sets forth propping agent of the present invention is intended to set forth rather than restriction the present invention.
Embodiment 1
Embodiment 1 is a propping agent formed according to the present invention.For forming embodiment 1, will gather carbodiimide coating and place on the particle, especially the particulate periphery.Embodiment 1 is compared with the contrast propping agent of Comparative Examples 1.
The composition of embodiment 1 is disclosed in the following table 1.In order to form embodiment 1, isocyanic ester A and catalyst A are mixed the formation reaction mixture.Add this reaction mixture and particle A in the reaction vessel and under 160 ℃ temperature, stir 20 minutes with polymeric isocyanate A.During stirring under these conditions, polymeric isocyanic ester A forms poly-carbodiimide coating on particle A.Afterwards, the particle A that is formed with poly-carbodiimide coating on it was heated 45 minutes under 200 ℃ temperature, promptly after fixing gathers carbodiimide coating to solidify, thereby obtains degree of crystallinity and hardness.Therefore, embodiment 1 is for comprising the particle A and the propping agent of the poly-carbodiimide coating of formation thereon.
Embodiment 1 is described in the following table 1.Amount in the table 1 is with the gram expression.
Table 1
| Embodiment 1 | |
| Isocyanic ester A | 15.79 |
| Catalyst A | 0.78 |
| Particle A | 300 |
Isocyanic ester A is
MI is with trade mark
The isocyanic ester of selling.
Catalyst A is 95 weight part Gamma Butyrolactones and 5 weight part 3-methyl isophthalic acid-phenyl-2-phospholene oxides.
Particle A is a 20/40Arizona sand.
Comparative Examples 1 is untreated 20/40Arizona sand propping agent.
The shatter strength of test implementation example 1 and Comparative Examples 1 and thermal characteristics.According to the shatter strength of API RP60 test implementation example 1, according to the shatter strength of API RP56 test comparison example 1.Stated the suitable formula of measuring the particulate percentage composition among API RP60 and the RP56.Also via the thermal characteristics of thermogravimetric analysis (TGA) test implementation example 1 and Comparative Examples 1.
10,000psi tests after the shatter strength down, and embodiment 1 has 4.7% particulate.On the contrary, 10,000psi tests after the shatter strength down, and Comparative Examples 1 has 27% particulate.Therefore, the shatter strength of embodiment 1 is significantly higher than Comparative Examples 1.When testing via TGA, embodiment 1 demonstrates excellent thermostability.Embodiment 1 surpass under 500 ℃ the temperature thermally-stabilised.
Embodiment 2-17
Embodiment 2-17 also is a propping agent formed according to the present invention.Embodiment 2-17 is formed by the disclosed component of table 2.Embodiment 2-17 comprises the propping agent that places the poly-carbodiimide coating on the particle A.By before applying poly-carbodiimide coating, particle A being activated with adhesion promotor A with adhesion promotor A precoating particle A.If the isocyanic ester of given embodiment comprises isocyanate mixture, then isocyanate mixture is acutely mixed.Be to form embodiment 2-17, isocyanic ester and catalyst A are added reaction vessel to form reaction mixture and with reaction mixture and be heated to 110 ℃ and kept 5 minutes.Afterwards, particle A is added in the reaction vessel and under the temperature of about 123 ℃ (about 250), stir and made concrete isocyanic ester or multiple isocyanic ester polymerization with (1) with the even coated particle A of reaction mixture and (2) in 6 minutes with reaction mixture.In case isocyanic ester or multiple isocyanic ester polymerization, then reaction mixture forms poly-carbodiimide coating on particle A.Therefore, embodiment 2-17 comprises particle A and the propping agent of the poly-carbodiimide coating that forms thereon.The propping agent of embodiment 2-15 is heated under 195 ℃ temperature, and promptly after fixing 3 hours is with the poly-carbodiimide coating of further curing.The propping agent of embodiment 16 and 17 is heated under 150 ℃ temperature, and promptly after fixing 3 hours is with the poly-carbodiimide coating of further curing.Following table 2 has been listed explanation and the test result of embodiment 2-17.Referring now to table 2:
The amount of isocyanic ester A-E is the weight percentage of isocyanic ester based on isocyanic ester combination gross weight;
Title is that the amount of the coating of coating Amt is the weight percentage of poly-carbodiimide coating based on the weight percentage of particle A, and
The amount of adhesion promotor A is the weight percentage of adhesion promotor based on the weight of poly-carbodiimide coating.
Table 2
Isocyanic ester B is
M20 is with trade mark
The isocyanic ester of selling.
Isocyanic ester C is
M is with trade mark
The isocyanic ester of selling.
Isocyanic ester D is
M70 is with trade mark
The isocyanic ester of selling.
Isocyanic ester E is
L5120 is with trade mark
The isocyanic ester of selling.
Adhesion promotor A is SILQUEST
TMA1100 is with trade mark SILQUEST
TMThe γ-An Jibingjisanyiyangjiguiwan of selling.
The shatter strength of embodiment 2-17 is passed through in test barrel in 9000PSI and 123 ℃ of compacting propping agent sample (its heavy 9.4 grams) tests down.After the compacting, measure particulate percentage composition and agglomeration.
Agglomeration is the objective observations of propping agent sample, the specific embodiment after the promptly above-mentioned shatter strength test.Press the value class of 1-10 and specify the propping agent sample.If the complete agglomeration of propping agent sample, grade are 10.If the not agglomeration of propping agent sample is promptly come off by tube behind the crushing test, grade is 1.Generally, preferred partial coalescence at least.
Reference table 2 discloses the shatter strength test comment afterwards of common description propping agent sample.How tightly packed comment be about propping agent sample and observations that how the propping agent sample is easily come off by test barrel in test barrel.
Embodiment 18 and 19
Embodiment 18 and 19 still is a propping agent formed according to the present invention.For forming embodiment 18 and 19, mix isocyanic ester and catalyst A and form reaction mixture.More specifically, with the 140g isocyanic ester with make the catalyst A that comprises the amount of 500ppm 3-methyl isophthalic acid-phenyl-2-phospholene oxides in the reaction mixture mix.Concrete isocyanic ester and consumption are disclosed in the table 3.Reaction mixture was heated 60 minutes and forms poly-carbodiimide coating down at 105 ℃.The poly-carbodiimide coating of molten state is cooled to similar thermoplastic crystal form of solidified and efflorescence.
The isocyanic ester of embodiment 18 and 19 has been described in the following table 3.Amount in the table 3 is the weight percentage based on isocyanic ester combination gross weight.
Table 3
| Embodiment 18 | Embodiment 19 | |
| |
0％ | 65％ |
| |
100％ | 35％ |
By before using poly-carbodiimide coating coating, particle A being activated with adhesion promotor A with adhesion promotor A precoating particle A.More specifically, to use based on 100 weight part particle A be the adhesion promotor A precoating of 0.25 weight % to particle A.To gather carbodiimide coating and particle A with 1: 20 weight ratio, it is 5% poly-carbodiimide coating based on 100 weight part particle A, adds in the reaction vessel, and stirs to form propping agent embodiment 18 and 19 being higher than under 110 ℃ the temperature.
Embodiment 18 and 19 is carried out crushing test, and the result of these tests is acceptable.In addition, the poly-carbodiimide coating of test implementation example 19 initial and under nitrogen, in anhydrous basically environment, store 1 month at ambient temperature after free NCO.The free NCO of original adoption example 19 is 14.58%, and the free NCO after month is 13.05%.Free NCO result shows that poly-carbodiimide coating is stable when storing at ambient temperature in anhydrous basically inert environments.By this stability, can be after forming poly-carbodiimide coating the propping agent of at least one month formation embodiment 19.In other words, poly-carbodiimide coating is still stablized and can be applied to particle with at least one month formation propping agent after forming poly-carbodiimide coating.
Embodiment 20-22
Embodiment 20-22 also is a propping agent formed according to the present invention.Embodiment 20-22 is formed by disclosed component in the table 4.Embodiment 20-22 comprises particle B and the propping agent of the poly-carbodiimide coating that forms thereon.In order to form embodiment 20-22, before with poly-carbodiimide coating coated particle B, pass through with adhesion promotor A precoating particle B and with particle B adhesion promotor A activation.Particle B is heated to 170 ℃ temperature.Mix isocyanic ester B, isocyanic ester C and catalyst A at ambient temperature to form reaction mixture.Afterwards, under 170 ℃ temperature, add particle B and reaction mixture in the reaction vessel and stir 2 minutes to form the propping agent of embodiment 20-22.During stirring, polyorganosiloxane release agent is injected on the propping agent further to guarantee not agglomeration of propping agent.After the stirring, the temperature that propping agent is heated to 170 ℃ kept 8 minutes.So, embodiment 20-22 formed after 10 minutes.Following table 4 has been described embodiment 20-22.Amount in the table 4 is with the gram expression.
Table 4
| |
Embodiment 21 | Embodiment 22 | |
| Isocyanic ester B | 5.229 | 4.482 | 2.265 |
| Isocyanic ester C | 2.241 | 2.988 | 2.625 |
| Catalyst A | 0.075 | 0.075 | 0.075 |
| Particle B | 200 | 200 | 141 |
| Adhesion promotor A | 0.08 | 0.08 | 0.056 |
Particle B is a 40/70Ottawa sand.Above listed other component.
10, the shatter strength of 000psi and 250 following test implementation example 20-22.Measure particulate percentage composition and agglomeration.After the shatter strength test, embodiment 20 has 1.9% particulate and is 2 according to the agglomeration of above-mentioned grade, and it is 3 that embodiment 21 has 0.9% particulate and agglomeration, and it is 4.5 that embodiment 22 has 1.7% particulate and agglomeration.Therefore, embodiment 20-22 shows excellent shatter strength in the agglomeration scope.
The present invention describes with exemplary approach, and should understand used term is descriptive language rather than restriction.Obviously, according to above-mentioned instruction, a lot of improvement of the present invention and modification are possible.Therefore, should understand in the scope of described claim, the present invention can put into practice unlike specifically described.
Claims (48)
1. the propping agent that is used for the hydraulic fracture stratum, described propping agent comprises:
A. particle; With
B. place the poly-carbodiimide coating on the described particle.
2. according to the propping agent of claim 1, wherein said poly-carbodiimide coating comprises the reaction product that isocyanic ester reacts in the presence of catalyzer.
3. according to the propping agent of claim 2, wherein said isocyanic ester is further defined as first isocyanic ester and is different from second isocyanic ester of described first isocyanic ester, makes described poly-carbodiimide coating comprise the reaction product of described first and second isocyanic ester.
4. according to the propping agent of claim 3, wherein said first isocyanic ester is further defined as polymeric isocyanate, and described second isocyanic ester is further defined as monomeric diisocyanate.
5. according to the propping agent of claim 4, wherein said polymeric isocyanate and described monomeric diisocyanate are with 4: 1-1: 4 weight ratio reaction forms described poly-carbodiimide coating.
6. according to the propping agent of claim 4, wherein said polymeric isocyanate and described monomeric diisocyanate are with 2.5: 1-1: 1 weight ratio reaction forms described poly-carbodiimide coating.
7. according to the propping agent of claim 4, wherein said polymeric isocyanate comprises the polymerization diphenylmethanediisocyanate and has the NCO content of about 31.5 weight %.
8. according to the propping agent of claim 4, wherein said monomeric diisocyanate comprises 4,4 '-diphenylmethanediisocyanate and have the NCO content of about 33.5 weight %.
9. according to the propping agent of claim 4, wherein in order to form described poly-carbodiimide coating, described polymeric isocyanate is with the quantitative response of the about 100 weight % of about 20-, and described monomeric diisocyanate is with the quantitative response of the about 80 weight % of about 20-, all based on the combination gross weight of described polymeric isocyanate and monomeric diisocyanate.
10. according to the propping agent of claim 2, wherein said catalyzer is selected from phosphorus compound, teritary amide, alkaline metal cpds, carboxylic metallic salt, non-alkaline organometallic compound and combination thereof.
11. according to the propping agent of claim 1, wherein said particle is selected from charcoal, mica, sawdust, wood chip, resin particle, polymer beads and the combination thereof of mineral, pottery, sand, nutshell, gravel, mill tailings, coal ash, rock, smelting, diatomite, crushing.
12. according to the propping agent of claim 1, it further comprises siliceous adhesion promotor.
13. according to the propping agent of claim 12, wherein said siliceous adhesion promotor is present in the described propping agent with the amount that serves as the about 10 weight % of about 0.001-based on the described poly-carbodiimide coating of 100 weight parts.
14. according to the propping agent of claim 1, it further comprises promoting agent.
15. according to the propping agent of claim 14, wherein said promoting agent is selected from microorganism, catalyzer and combination thereof.
16. according to the propping agent of claim 1, wherein said poly-carbodiimide coating is serving as that the amount of the about 10 weight % of about 0.1-is present in the described propping agent based on the described particle of 100 weight parts.
17. according to the propping agent of claim 1, its be higher than under 100 ℃ the temperature thermally-stabilised.
18. according to the propping agent of claim 1, its shatter strength of measuring under the pressure of 7500-15000psi according to American Petroleum Institute (API) RP60 is 15% or maximum particulate still less.
19. be formed for the method for the propping agent on hydraulic fracture stratum, said method comprising the steps of:
A., particle is provided;
B., poly-carbodiimide coating is provided; With
C. with poly-carbodiimide coating coated particle.
20. according to the method for claim 19, it further comprises makes isocyanic ester react the step that forms poly-carbodiimide coating in the presence of catalyzer.
21. method according to claim 20, wherein isocyanic ester is further defined as first isocyanic ester and be different from second isocyanic ester of first isocyanic ester, and the step of isocyanate reaction is further defined as make first and second isocyanic ester react formation in the presence of catalyzer and gathers carbodiimide coating.
22. method according to claim 21, wherein first isocyanic ester is further defined as polymeric isocyanate, second isocyanic ester is further defined as monomeric diisocyanate, and the step of first and second isocyanate reactions is further defined as polymeric isocyanate and monomeric diisocyanate are reacted in the presence of catalyzer and forms poly-carbodiimide coating.
23. according to the method for claim 22, the step that polymeric isocyanate and monomeric diisocyanate are reacted is further defined as and makes polymeric isocyanate and monomeric diisocyanate with 4: 1-1: 4 weight ratio reaction forms poly-carbodiimide coating.
24. according to the method for claim 22, the step that polymeric isocyanate and monomeric diisocyanate are reacted is further defined as and makes polymeric isocyanate and monomeric diisocyanate with 2.5: 1-1: 1 weight ratio reaction forms poly-carbodiimide coating.
25. according to the method for claim 19, it further is included in before the step of using poly-carbodiimide coating coated particle or simultaneously particle is heated above the step of 150 ℃ temperature.
26., isocyanic ester is reacted form the step of poly-carbodiimide coating and in 20 minutes or shorter time, carry out jointly under catalyst action with the step of gathering carbodiimide coating coated particle according to the method for claim 20.
27. according to the method for claim 20, the step that wherein makes isocyanate reaction form poly-carbodiimide coating was carried out before the step with poly-carbodiimide coating coated particle.
28. according to the method for claim 20, the step that wherein makes isocyanate reaction form poly-carbodiimide coating is carried out simultaneously with the step of using poly-carbodiimide coating coated particle.
29. according to the method for claim 28, it further is included in the isocyanate reaction that makes that carries out simultaneously and forms poly-carbodiimide coating and with the step of poly-carbodiimide coating coated particle before or simultaneously particle is heated above the step of 150 ℃ temperature.
30. according to the method for claim 29, it further comprises the step of heating propping agent with further crosslinked poly-carbodiimide coating.
31. according to the method for claim 30, wherein make isocyanate reaction form poly-carbodiimide coating step, in 30 minutes or shorter time, carry out jointly with the step of further crosslinked poly-carbodiimide coating with the step of poly-carbodiimide coating coated particle and heating propping agent.
32. according to the method for claim 19, it further comprises the step of heating propping agent with further crosslinked poly-carbodiimide coating.
33. according to the method for claim 22, wherein polymeric isocyanate comprises the polymerization diphenylmethanediisocyanate and has the NCO content of about 31.5 weight %.
34. according to the method for claim 22, wherein monomeric diisocyanate comprises 4,4 '-diphenylmethanediisocyanate and have the NCO content of about 33.5 weight %.
35. according to the method for claim 19, wherein particle is selected from charcoal, mica, sawdust, wood chip, resin particle, polymer beads and the combination thereof of mineral, pottery, sand, nutshell, gravel, mill tailings, coal ash, rock, smelting, diatomite, crushing.
36. limit the method on the stratum of underground conservation pool with the mixture hydraulic fracture that comprises carrier fluid and propping agent, wherein propping agent comprises particle and places poly-carbodiimide coating on the described particle, and described method comprises described mixture is pumped in the underground conservation pool to cause the step of stratum splitting.
37. according to the method for claim 36, wherein poly-carbodiimide coating comprises the reaction product that isocyanic ester reacts in the presence of catalyzer.
38. according to the method for claim 37, wherein isocyanic ester is further defined as first isocyanic ester and second isocyanic ester that is different from first isocyanic ester, makes poly-carbodiimide coating comprise the reaction product of first and second isocyanic ester.
39. according to the method for claim 38, wherein first isocyanic ester is further defined as polymeric isocyanate, and second isocyanic ester is further defined as monomeric diisocyanate.
40. according to the method for claim 39, wherein polymeric isocyanate and monomeric diisocyanate are with 4: 1-1: 4 weight ratio reaction forms poly-carbodiimide coating.
41. according to the method for claim 39, wherein polymeric isocyanate and monomeric diisocyanate are with 2.5: 1-1: 1 weight ratio reaction forms poly-carbodiimide coating.
42. according to the method for claim 39, wherein polymeric isocyanate comprises the polymerization diphenylmethanediisocyanate and has the NCO content of about 31.5 weight %.
43. according to the method for claim 39, wherein monomeric diisocyanate comprises 4,4 '-diphenylmethanediisocyanate and have the NCO content of about 33.5 weight %.
44. according to the method for claim 36, wherein particle is selected from charcoal, mica, sawdust, wood chip, resin particle, polymer beads and the combination thereof of mineral, pottery, sand, nutshell, gravel, mill tailings, coal ash, rock, smelting, diatomite, crushing.
45. according to the method for claim 36, wherein propping agent be higher than under 100 ℃ the temperature thermally-stabilised.
46. according to the method for claim 36, wherein the shatter strength measured under the pressure of 7500-15000psi according to American Petroleum Institute (API) RP60 of propping agent is 15% or maximum particulate still less.
47. according to the method for claim 36, it comprises that further preparation comprises the step of the mixture of carrier fluid and propping agent.
48. according to the method for claim 36, it further is included in the step of using the propping agent filtered fluid in the underground conservation pool.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10922608P | 2008-10-29 | 2008-10-29 | |
| US61/109,226 | 2008-10-29 | ||
| US22909309P | 2009-07-28 | 2009-07-28 | |
| US61/229,093 | 2009-07-28 | ||
| PCT/EP2009/064244 WO2010049467A1 (en) | 2008-10-29 | 2009-10-29 | A proppant |
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| CN102203211A true CN102203211A (en) | 2011-09-28 |
| CN102203211B CN102203211B (en) | 2013-12-18 |
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| CN2009801432762A Expired - Fee Related CN102203211B (en) | 2008-10-29 | 2009-10-29 | Proppant |
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| EP (1) | EP2350228A1 (en) |
| CN (1) | CN102203211B (en) |
| AR (1) | AR073417A1 (en) |
| AU (1) | AU2009309692B2 (en) |
| BR (1) | BRPI0919963A2 (en) |
| EA (1) | EA023407B1 (en) |
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| CA2606541C (en) | 2007-06-28 | 2012-07-10 | M-I Llc | Degradable gels in zonal isolation applications |
| EP2247702B1 (en) | 2008-01-18 | 2013-11-06 | M-I L.L.C. | Degradable non-aqueous gel systems |
| DE102008000352A1 (en) | 2008-02-20 | 2009-08-27 | Rhein Chemie Rheinau Gmbh | Cast polyamide preparation using special activators |
| EA023407B1 (en) | 2008-10-29 | 2016-06-30 | Басф Се | Proppant for hydraulic fracturing of a subterranean formation |
-
2009
- 2009-10-29 EA EA201100710A patent/EA023407B1/en not_active IP Right Cessation
- 2009-10-29 MY MYPI2011001834A patent/MY165277A/en unknown
- 2009-10-29 AR ARP090104176A patent/AR073417A1/en active IP Right Grant
- 2009-10-29 BR BRPI0919963A patent/BRPI0919963A2/en not_active Application Discontinuation
- 2009-10-29 AU AU2009309692A patent/AU2009309692B2/en not_active Ceased
- 2009-10-29 CN CN2009801432762A patent/CN102203211B/en not_active Expired - Fee Related
- 2009-10-29 WO PCT/EP2009/064244 patent/WO2010049467A1/en active Application Filing
- 2009-10-29 EP EP09752319A patent/EP2350228A1/en not_active Withdrawn
- 2009-10-29 US US13/126,905 patent/US9719011B2/en not_active Expired - Fee Related
-
2011
- 2011-05-24 EC EC2011011078A patent/ECSP11011078A/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| CN102203211B (en) | 2013-12-18 |
| AR073417A1 (en) | 2010-11-03 |
| US20110297383A1 (en) | 2011-12-08 |
| MY165277A (en) | 2018-03-20 |
| EP2350228A1 (en) | 2011-08-03 |
| EA201100710A1 (en) | 2011-12-30 |
| BRPI0919963A2 (en) | 2015-12-08 |
| AU2009309692B2 (en) | 2015-02-05 |
| US9719011B2 (en) | 2017-08-01 |
| WO2010049467A1 (en) | 2010-05-06 |
| AU2009309692A1 (en) | 2010-05-06 |
| EA023407B1 (en) | 2016-06-30 |
| ECSP11011078A (en) | 2011-06-30 |
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